CN102750998A - Transparent graphene conductive thin film and preparation method thereof - Google Patents
Transparent graphene conductive thin film and preparation method thereof Download PDFInfo
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- CN102750998A CN102750998A CN2012102351874A CN201210235187A CN102750998A CN 102750998 A CN102750998 A CN 102750998A CN 2012102351874 A CN2012102351874 A CN 2012102351874A CN 201210235187 A CN201210235187 A CN 201210235187A CN 102750998 A CN102750998 A CN 102750998A
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Abstract
The invention discloses a transparent graphene conductive thin film and a preparation method of the film, aiming at improving the acid and alkali resistance of a transparent conductive thin film. The transparent graphene conductive thin film is a graphene thin film with the thickness of 1-50nm and the electrical conductivity of 300-800S/cm, and has the light transmittance of 70-85% for light with the wavelength within the range of 200-1100nm. The preparation method of the transparent graphene conductive thin film comprises the steps of: oxidizing graphite, preparing a graphene oxide water mixed liquid, preparing a graphene oxide thin film, and reducing to obtain the transparent graphene conductive thin film. Compared with the prior art, the transparent graphene conductive thin film which is prepared by a high-temperature reduction or chemical reduction method has the advantages of being good in light transmittance and electrical conductivity, large in preparation area, simple in preparation method and low in cost; and the transparent graphene conductive thin film can be used for replacing the traditional inorganic oxide electrode material indium tin oxide (ITO), thus providing infinite space for the transparent conductive thin film and the related fields.
Description
Technical field
The present invention relates to a kind of transparent conductive film and preparation method thereof, particularly a kind of transparent conductive film based on Graphene and preparation method thereof.
Technical background
The present application of transparent conductive film is very wide, such as the transparency electrode of solar cell, and the electro-conductive glass of touch-screen etc.The material that is used for making the transparent conductive film comparative maturity now is tin indium oxide ITO.Yet there is following shortcoming in it: the content of indium is very rare on the earth, annual underproduce 500 tons, and need from the zinc lead ore, extract, cause the ITO cost high; Under acid and alkaline environment, the metal ion of ITO tends to be diffused into polymeric layer, causes it very unstable, and limited to the transmitance of light near infrared region.
Summary of the invention
The purpose of this invention is to provide a kind of Graphene transparent conductive film and preparation method thereof, the technical problem that solve is to improve the resistance to acids and bases of transparent conductive film, and reduces cost.
The present invention adopts following technical scheme: a kind of Graphene transparent conductive film, said Graphene transparent conductive film are the graphene film of 1 ~ 50nm, and conductivity is 300 ~ 800S/cm, are 70 ~ 85% to wavelength at the light transmittance of the light of 200 ~ 1100nm.
A kind of preparation method of Graphene transparent conductive film may further comprise the steps: one, graphite oxide, press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer; Graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, and the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml, after stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, adds strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension; Add deionized water; Temperature of charge is brought up to 96 ± 1 ℃, react 1h, add 30% H again
2O
2, filtering precipitate does not have acid group with deionized water wash in filtrating, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake; Said strong oxidizer is potassium hyperchlorate and/or potassium permanganate; Two, preparation graphene oxide water mixed liquid adds graphite oxide filter cake, frequency 1-20KHz in pure water; Power 400-3000w, sonic oscillation 10-30min under the room temperature, centrifugal treating; Rotating speed is 500-6000rpm, and the time is 1-30min, removes the graphene oxide lamella more than 5 layers; Obtain the graphene oxide water mixed liquid, content is 0.01 ~ 1mg/mL; Three, the preparation graphene oxide film adopts spraying with graphene oxide liquid mixture, spin coating, and dip-coating is dripped coating method and on substrate, is obtained the graphene oxide film that thickness is 1-50nm; Four, adopt the method for high temperature reduction or electronation to obtain the Graphene transparent conductive film that thickness is 1 ~ 50nm.
Method of the present invention obtains being warming up to stirring reaction 3h between 30-40 ℃ behind the suspension, adds deionized water then.
Graphite powder is a natural flake graphite in the method for the present invention, natural modified graphite, and Delanium, more than one in the expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m.
Method middle strong acidity solution of the present invention is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.
Centrifugal treating is divided and is carried out for three times in the method for the present invention, removes the graphite oxide filter cake of not peeling off fully as yet for the first time, for the second time supernatant liquor is centrifugalized, and for the third time the sediment after centrifugal is centrifugalized after with distilled water diluting again.
Spraying is that substrate is preheating to 50 ~ 80 ℃ in the method for the present invention, with spray gun graphene oxide liquid mixture is sprayed on the substrate, and moisture content obtains graphene oxide film after volatilizing naturally; Said spin coating is to let substrate rotate with the 2000-5000rpm rotating speed; Time 5min; Graphene oxide liquid mixture is dripped on the substrate, graphene oxide liquid mixture is is evenly spread out and put at substrate surface, directly at 50 ~ 80 ℃ of dry 10min-2h; Naturally cool to room temperature then, obtain graphene oxide film after the drying; Said dip-coating is that substrate is immersed 5 ~ 60min in the graphene oxide liquid mixture, directly at 50 ~ 80 ℃ of drying 5 ~ 60min, naturally cools to room temperature then; Said is coated with is that the graphene oxide liquid mixture drop is directly dropped on the substrate, treat that graphene oxide liquid mixture is spread out and put on out fully after, directly, naturally cool to room temperature then at 50-80 ℃ of dry 5-60min.
High temperature reduction in the method for the present invention, vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen and acetylene gas; At capacity is in the reacting furnace of 5 ~ 10L; Flow is 50 ~ 200sccm, with the programming rate of 1-30 ℃/min, is warming up to 200 ~ 1100 ℃; 0＜time≤7h, naturally cool to room temperature in the stove then; Electronation; Temperature is 70 ~ 90 ℃; Graphene oxide film is placed reducing agent steam, and in volume was the reaction vessel of 10 ~ 30L, steam flow was 20 ~ 200sccm; Time is no less than 1h, and reducing agent is more than one in hydrazine hydrate, hydrogen iodide, concentrated ammonia liquor, Dimethylhydrazine, sodium dithionite, sodium borohydride and the potassium borohydride.
Nitrogen, argon gas, helium in the method for the present invention, temperature rise to 700 ~ 1100 ℃; Said hydrogen, acetylene, temperature rise to 200 ~ 700 ℃.
A kind of preparation method of Graphene transparent conductive film may further comprise the steps: one, graphite oxide, press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer; Graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, and the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml, after stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, adds strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension; Be warming up to stirring reaction 3h between 30-40 ℃, add deionized water, temperature of charge is brought up to 96 ± 1 ℃; React 1h, add 30% H again
2O
2, filtering precipitate, with deionized water fully wash until filtrating in do not have acid group, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake; Said graphite powder is a natural flake graphite, natural modified graphite, and Delanium, more than one in the expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m; Said strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%; Said strong oxidizer is potassium hyperchlorate and/or potassium permanganate; Two, graphite oxide reduces, and takes the method for high temperature solid-state reduction or liquid phase chemical reduction, obtains Graphene; Said high temperature reduction with the graphite oxide filter cake, directly toasts 2 ~ 10h down at 50 ~ 80 ℃, is crushed to D
50Be 1 ~ 20um; In vacuum environment, or in more than one atmosphere in the nitrogen, argon gas, helium, hydrogen, acetylene gas, be in 5 ~ 10L reacting furnace at volume; Gas flow is 20 ~ 200sccm; Directly high temperature reduction 10s ~ 10min in 900 ~ 1100 ℃ naturally cools to room temperature in the stove then, obtains Graphene; Said liquid-phase reduction is pressed graphite oxide filter cake, 80% concentration hydrazine hydrate mass ratio 0.7:1, and graphite oxide filter cake and hydrazine hydrate are mixed directly at 70 ~ 90 ℃; Rotating speed 30 ~ 100rpm, reaction reductase 12 ~ 10h obtains Graphene solution; Filter then and obtain Graphene; With pure water washing and filtering thing 3 ~ 6 times, obtain the Graphene slurries at last, obtain Graphene by the prior art drying; Three, the preparation of graphene film is mixed with the Graphene mixed liquor of 0.05 ~ 1mg/ml by Graphene, organic solvent, and the Graphene mixed liquor is adopted spraying, spin coating, and dip-coating is dripped a coating method and is obtained the Graphene transparent conductive film that thickness is 1 ~ 50nm; Said organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, butanone.
The present invention compared with prior art adopts the method for high temperature reduction or electronation to prepare the Graphene transparent conductive film, and it is good to have a light penetrability; Conductivity is good; The preparation area is big, and the preparation method is simple, the advantage that cost is low; Graphene transparent conductive film of the present invention is expected to replace traditional inorganic oxide electrode material ITO, for the development of transparent conductive film and association area provides immensity.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.Graphene transparent conductive film of the present invention, adopting thickness is the graphene film of 1 ~ 50nm, conductivity is 300 ~ 800S/cm, is 70 ~ 85% to wavelength at the light transmittance of the light of 200 ~ 1100nm.
The preparation method of Graphene transparent conductive film of the present invention adopts graphite oxide, disperses, and the preparation graphene oxide film, reduction may further comprise the steps:
One, graphite oxide; Press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer, graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml; After stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, add strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension.Be warming up to stirring reaction 3h between 30-40 ℃.Add deionized water then, temperature of charge is brought up to 96 ± 1 ℃, react 1h, add 30% H again
2O
2, suspension becomes sediment and glassy yellow liquid, filtering precipitate, with deionized water fully wash until filtrating in do not have acid group, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake.
Graphite powder is a natural flake graphite, natural modified graphite, and Delanium, more than one in the expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m.
Strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.
Strong oxidizer is potassium hyperchlorate and/or potassium permanganate.
Two, preparation graphene oxide water mixed liquid adds graphite oxide filter cake, frequency 1-20KHz in pure water; Power 400-3000w, sonic oscillation 10-30min under the room temperature makes the graphite oxide filter cake be stripped from into the graphene oxide lamella of 1-100 layer; Centrifugal treating can be divided and carried out for three times then, removes the graphite oxide filter cake of not peeling off fully as yet for the first time; For the second time supernatant liquor is centrifugalized, for the third time the sediment after centrifugal is centrifugalized after with distilled water diluting again, three times rotating speed is 500-6000rpm; Centrifugal treating total time is 1-30min; Remove the graphene oxide lamella more than 5 layers, obtain the graphene oxide lamella and be dispersed in the graphene oxide liquid mixture in the water, content is 0.01 ~ 1mg/mL.
Three, the preparation graphene oxide film adopts spraying with graphene oxide liquid mixture, spin coating, and dip-coating is dripped coating method and on substrate, is obtained the graphene oxide film that thickness is 1-50nm.
Spraying is that substrate is preheating to 50 ~ 80 ℃, with spray gun graphene oxide liquid mixture is sprayed on the substrate, and moisture content obtains graphene oxide film after volatilizing naturally.
Spin coating is to let substrate rotate with the 2000-5000rpm rotating speed; Time 5min; Graphene oxide liquid mixture is dripped on the substrate, graphene oxide liquid mixture is is evenly spread out and put at substrate surface, directly at 50 ~ 80 ℃ of dry 10min-2h; Naturally cool to room temperature then, obtain graphene oxide film after the drying.Regulate the rotating speed of substrate and can control the speed of spreading out and putting on and uniformity.
Dip-coating is that substrate is immersed 5 ~ 60min in the graphene oxide liquid mixture, after immersion is accomplished substrate is taken out, and directly at 50 ~ 80 ℃ of drying 5 ~ 60min, naturally cools to room temperature then, and this mode is applicable to the special graphene oxide film of preparation substrate shape.
Drip that to be coated be that the graphene oxide liquid mixture drop is directly dropped on the substrate, treat that graphene oxide liquid mixture is spread out and put on out fully after, directly, naturally cool to room temperature then at 50-80 ℃ of dry 5-60min.The concentration of this mode mixed liquor is got less.
Substrate can be transparency silica glass, transparent organic film, Al as bearing basement
2O
3Film, smooth sheet metal or smooth nonmetal hard sheet are of a size of 1 ~ 10 inch of diameter.Sheet metal is gold, silver, aluminium, copper, nickel, and nonmetal is silicon dioxide, plastics, wood chip.
Four, reduction preparation graphene film adopts the method for high temperature reduction or electronation to obtain the graphene film that thickness is 1 ~ 50nm, i.e. Graphene transparent conductive film.
High temperature reduction, vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen and acetylene gas; At capacity is in the reacting furnace of 5 ~ 10L, and flow is 50 ~ 200sccm, with the programming rate of 1-30 ℃/min; Be warming up to 200～1100 ℃; 0＜time≤7h naturally cools to room temperature in the stove then, and it is exotic material that the method is used for substrate.When if atmosphere is non-reducing gas; Such as nitrogen, argon gas, helium, temperature rises to 700 ~ 1100 ℃, and the hydrogen atom in the oxygen atom in the graphene oxide molecular structure and its molecular structure combines; Generate steam; Carbon atom in oxygen atom in the graphene oxide molecular structure and its molecular structure combines, and generates carbon dioxide, the graphene oxide reduction.If atmosphere is reducibility gas, such as hydrogen, acetylene, temperature rises to 200 ~ 700 ℃, and oxy radical meeting and the combination of reducibility gas atom in the graphite oxide molecular structure generate water and carbon dioxide, the graphene oxide reduction.
Electronation, temperature are 70 ~ 90 ℃, and graphene oxide film is placed reducing agent steam, and in volume was the reaction vessel of 10 ~ 30L, steam flow was 20 ~ 200sccm, and the time is no less than 1h.Electronation is through reducing agent the oxygen-containing functional group on the graphite oxide molecular structure to be removed, thus redox graphene.
Reducing agent is more than one in hydrazine hydrate, hydrogen iodide, concentrated ammonia liquor, Dimethylhydrazine, sodium dithionite, sodium borohydride and the potassium borohydride.
The preparation method of Graphene transparent conductive film of the present invention adopts graphite oxidation, reduction, and the preparation graphene film may further comprise the steps:
One, graphite oxide; Press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer, graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml; After stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, add strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension.Be warming up to stirring reaction 3h between 30-40 ℃.Add deionized water then, temperature of charge is brought up to 96 ± 1 ℃, react 1h, add 30% H again
2O
2, suspension becomes sediment and glassy yellow liquid, filtering precipitate, with deionized water fully wash until filtrating in do not have acid group, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake.
Graphite powder is a natural flake graphite, natural modified graphite, and Delanium, more than one in the expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m.
Strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.
Strong oxidizer is potassium hyperchlorate and/or potassium permanganate.
Two, graphite oxide reduces, and takes the method for high temperature solid-state reduction or liquid phase chemical reduction, obtains Graphene.
High temperature reduction with the graphite oxide filter cake, directly toasts 2 ~ 10h down at 50 ~ 80 ℃, is crushed to D
50Be 1 ~ 20um; In vacuum environment, or in more than one atmosphere in the nitrogen, argon gas, helium, hydrogen, acetylene gas, be in 5 ~ 10L reacting furnace at volume; Gas flow is 20 ~ 200sccm; Directly high temperature reduction 10s ~ 10min in 900 ~ 1100 ℃ naturally cools to room temperature in the stove then, obtains Graphene.
Liquid-phase reduction is pressed graphite oxide filter cake, 80% concentration hydrazine hydrate mass ratio 0.7:1, and graphite oxide filter cake and hydrazine hydrate are mixed directly at 70 ~ 90 ℃; Rotating speed 30 ~ 100rpm, reaction reductase 12 ~ 10h obtains Graphene solution; Filter then and obtain Graphene; With pure water washing and filtering thing 3 ~ 6 times, obtain the Graphene slurries at last, obtain Graphene by the prior art drying.
Three, the preparation of graphene film is mixed with the Graphene mixed liquor of 0.05 ~ 1mg/ml by Graphene, organic solvent, and the Graphene mixed liquor is adopted spraying; Spin coating; Dip-coating is dripped coating method and is obtained the graphene film that thickness is 1 ~ 50nm, i.e. Graphene transparent conductive film.
Spraying is that substrate is preheating to 50 ~ 80 ℃, with spray gun the Graphene mixed liquor is sprayed on the substrate, and solvent obtains graphene oxide film after volatilizing naturally.
Spin coating is to let substrate rotate with the 2000-5000rpm rotating speed; The Graphene mixed liquor is dripped on the substrate, the Graphene mixed liquor is is evenly spread out and put at substrate surface, directly at 50 ~ 80 ℃ of drying 10 ~ 30min; Naturally cool to room temperature then, obtain graphene film after the drying.Regulate the rotating speed of substrate and can control the speed of spreading out and putting on and uniformity.
Dip-coating is that substrate is immersed 5 ~ 60min in the Graphene mixed liquor, after immersion is accomplished substrate is taken out, and directly at 50 ~ 80 ℃ of drying 5 ~ 60min, naturally cools to room temperature then, and this mode is applicable to the special graphene film of preparation substrate shape.
Drip that to be coated be that Graphene mixed liquor drop is directly dropped on the substrate, treat that the Graphene mixed liquor is spread out and put on out fully after, directly, naturally cool to room temperature then at 50 ~ 80 ℃ of drying 5 ~ 60min.The concentration of this mode mixed liquor is got less.
Organic solvent is an alcohols, ketone or N-methyl pyrrolidone NMP.Alcohols is the less methyl alcohol of molecular weight, ethanol, propyl alcohol, and ketone is acetone, butanone.
Substrate can be transparency silica glass, transparent organic film, Al as bearing basement
2O
3Film, smooth sheet metal or smooth nonmetal hard sheet are of a size of 1 ~ 10 inch of diameter.
The Graphene transparent conductive film of the inventive method preparation; Using the U.S. di D3100 of Veeco company AFM to survey film thickness is 1 ~ 50nm; Using U.S. Midwest company's T P28-SZT-2000 four point probe conductivity measurement to record conductivity is 300 ~ 800 S/cm, and recording wavelength with the U.S. F10-RT-UV of FILMETRICS company type light transmittance detector is 70-85% at the light transmittance of 200 ~ 1100nm.
Prepared graphene transparent conductive film of the present invention; Under the wavelength of 500nm; Light permeable rate is more than 70%, and conductance can be used as electrode of solar battery, touch-screen conductive film greater than 500S/cm; Be expected to replace traditional inorganic oxide electrode material ITO, for the development of transparent conductive film and association area provides immensity.
Embodiment 1,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 200ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the graphite oxide filter cake is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 1mg/mL.
Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 4000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light brown film of coating, thickness 3nm.
Four, above-mentioned film is put into the program control high temperature furnace of capacity 5L, fed argon gas, flow 200sccm, heating rate are 30 ℃/min, and temperature is controlled at 1000 ℃ after rising, reaction 30min.Take out behind the natural cooling and promptly obtain graphene film.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 80%, and conductance is 600S/cm.
Embodiment 2,
One, under the room temperature, be that 70% concentrated sulfuric acid solution 300ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 0.5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 60g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the graphite oxide filter cake is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 20KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 5000rpm and 5min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL.
Three, adopt the mode of spin coating that above-mentioned solution is applied on the quartz substrate, spin speed is 5000rpm.Rotational time 5min, oven dry 2h is subsequent use under 70 ℃ in baking oven.The film that makes is the uniform light brown film of coating, thickness 4nm.
Four, above-mentioned film is put into the program control high temperature furnace of capacity 10L, fed nitrogen, flow 300sccm, heating rate are 30 ℃/min, and temperature is controlled at 1000 ℃ after rising, reaction 30min.Take out behind the natural cooling and promptly obtain graphene film.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 71%, and conductance is 500S/cm.
Embodiment 3,
One, under the room temperature, be that 80% concentrated sulfuric acid solution 250ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 50g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the graphite oxide filter cake is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 10KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 5000rpm and 5min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 0.1mg/mL.
Three, adopt to drip the mode that is coated with above-mentioned mixing drop at the bottom of the silicon wafer-based, drip the amount of being coated with and be controlled at 2 μ L, treat drop fully after spreading out in the substrate, direct 70 ℃ of oven dry 2h down in baking oven, natural cooling is subsequent use.The film that makes is the uniform light brown film of coating, thickness 5nm.
Four, above-mentioned film is put into the program control high temperature furnace of capacity 8L, fed hydrogen, flow 200sccm, heating rate are 30 ℃/min, and temperature is controlled at 1000 ℃ after rising, reaction 10min.Take out behind the natural cooling and promptly obtain graphene film.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 74%, and conductance is 480S/cm.
Embodiment 4,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the oxidized graphite flake layer that will pulverize after grinding disperses in water, and the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL.
Three, adopt to drip the mode that is coated with above-mentioned mixing drop at the bottom of the silicon wafer-based, drip the amount of being coated with and be controlled at 2 μ L, treat drop fully after spreading out in the substrate, direct 70 ℃ of oven dry 2h down in baking oven, natural cooling is subsequent use.The film that makes is the uniform light brown film of coating, thickness 5nm.
Four, above-mentioned film is put into the program control high temperature furnace of capacity 10L, fed argon gas, flow 200sccm, heating rate are 30 ℃/min, and temperature is controlled at 1000 ℃ after rising, reaction 30min.Take out behind the natural cooling and promptly obtain graphene film.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 510S/cm.
Embodiment 5,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the graphite oxide filter cake is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 5000rpm and 5min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 0.01mg/mL.
Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 5000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light brown film of coating, thickness 5nm.
Four, above-mentioned film being put into the reacting furnace of capacity 10L, was under the condition below the 1Pa in vacuum degree, and programming rate is 20 ℃/min, 1000 ℃ of reactions 3 hours.Take out behind the natural cooling and promptly obtain graphene film.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 505 S/cm, and conductance is 510 S/cm.
Embodiment 6,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, the oxidized graphite flake layer that will pulverize after grinding disperses in water, and the ultrasonic oxidized graphite flake layer of peeling off obtains graphene oxide liquid mixture a little less than the utilization.Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is centrifugalized, at first remove the oxidized graphite flake layer of not peeling off fully as yet, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 5000rpm and 5min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, be configured to the graphene oxide liquid mixture that concentration is 0.05mg/mL.
Three, adopt the mode of spraying that above-mentioned mixed liquor is applied on the quartz substrate, discharge rate is 5ml, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light brown film of coating, thickness 3nm.
Four, the graphene oxide film that above-mentioned reaction is obtained; Placing volumetric concentration is 5% hydrazine hydrate (or hydrogen iodide) steam, and in the reaction vessel of capacity 10L, temperature is that 80 ℃ of steam flows are 50sccm; Reaction time is 1h, promptly gets graphene film after taking-up is dried.The light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 72%, and conductance is 515S/cm.
Embodiment 7,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 200ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake, and crushed after being dried is ground to granularity less than 50um.
Two, 3g left and right sides graphite oxide powder is put into the program control high temperature furnace about capacity 5L, feed argon gas, flow 200sccm, heating rate are 2000 ℃/min, and temperature rises to 1000 ℃, reaction 30s.Take out behind the natural cooling and promptly obtain graphene powder.
Three, graphene powder is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains the Graphene mixed liquor a little less than the utilization.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is centrifugalized, at first remove the Graphene lamella of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL.
Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 4000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light grey semitransparent thin film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 80%, and conductance is 600S/cm.
Embodiment 8,
One, under the room temperature, be that 70% concentrated sulfuric acid solution 300ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 0.5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 60g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake, and crushed after being dried is ground to granularity less than 50um.
Two, 3g left and right sides graphite oxide powder is put into the program control high temperature furnace about capacity 10L, feed argon gas, flow 400sccm, heating rate are 2000 ℃/min, and temperature rises to 1000 ℃, reaction 30s.Take out behind the natural cooling and promptly obtain graphene powder.
Three, graphene powder is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains the Graphene mixed liquor a little less than the utilization.Its medium frequency 20KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is centrifugalized, at first remove the Graphene lamella of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL.
Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 4000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light grey semitransparent thin film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 71%, and conductance is 500S/cm.
Embodiment 9,
One, under the room temperature, be that 80% concentrated sulfuric acid solution 250ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 50g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake, and crushed after being dried is ground to granularity less than 50um.
Two, 3g left and right sides graphite oxide powder is put into the program control high temperature furnace about capacity 10L, feed argon gas, flow 400sccm, heating rate are 2000 ℃/min, and temperature rises to 1000 ℃, reaction 30s.Take out behind the natural cooling and promptly obtain graphene powder.
Three, graphene powder is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains the Graphene mixed liquor a little less than the utilization.Its medium frequency 10KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is centrifugalized, at first remove the Graphene lamella of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, and being configured to concentration is the Graphene mixed liquor of 0.05mg/mL.
Four, adopt to drip the mode that is coated with above-mentioned mixing drop at the bottom of the silicon wafer-based, drip the amount of being coated with and be controlled at 2mL, treat drop fully after spreading out in the substrate, direct 70 ℃ of oven dry 2h down in baking oven, natural cooling is subsequent use.The film that makes is the uniform light grey semitransparent thin film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 74%, and conductance is 580S/cm.
Embodiment 10,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 70 ℃ rotating speed 50rpm; Reaction reduction 10 h; Obtain Graphene solution, filter then and obtain Graphene, with pure water washing and filtering thing 3 ~ 6 times; Add pure water at last and obtain Graphene solution, concentration is 0.5mol/ml.
Three, adopt to drip the mode that is coated with above-mentioned mixing drop at the bottom of the silicon wafer-based, drip the amount of being coated with and be controlled at 2mL, treat drop fully after spreading out in the substrate, direct 70 ℃ of oven dry 2h down in baking oven, natural cooling is subsequent use.The film that makes is the uniform light grey semitransparent thin film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 800S/cm.
Embodiment 11,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake.
Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 90 ℃ rotating speed 60rpm; Reaction reductase 12 h; Obtain Graphene solution, filter then and obtain Graphene, with pure water washing and filtering thing 3 ~ 6 times; Add pure water at last and obtain Graphene solution, concentration is 1mol/ml.
Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 5000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light grey film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 505S/cm, and conductance is 710S/cm.
Embodiment 12,
One, under the room temperature, be that 98% concentrated sulfuric acid solution 230ml places container with concentration, ice bath control temperature is at 0 ℃; Add 10g natural flake graphite and 5g sodium nitrate; Mixing speed is controlled at 600rpm, stirs 30min, again to wherein slowly adding 30g strong oxidizer KMnO
4, continuing to stir 2h, control reaction temperature obtains suspension being no more than 10 ℃.Be warming up to 35 ℃ of stirring reaction 3h.The adding deionized water is brought up to 96 ± 1 ℃ with temperature of charge, and reaction 1h, use deionized water are 30% H with reactant solution dilution back adding volumetric concentration
2O
2, filtering precipitate does not have SO with deionized water washing sediment to filtrating while hot
4 2-, vacuum dehydration obtains the graphite oxide filter cake, and crushed after being dried is ground to granularity less than 50um.
Two, 3g left and right sides graphite oxide powder is put into the program control high temperature furnace about capacity 10L, feed argon gas, flow 400sccm, heating rate are 2000 ℃/min, and temperature rises to 1000 ℃, reaction 30s.Take out behind the natural cooling and promptly obtain graphene powder.
Three, graphene powder is disperseed in water, the ultrasonic oxidized graphite flake layer of peeling off obtains the Graphene mixed liquor a little less than the utilization.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is centrifugalized, at first remove the Graphene lamella of not peeling off fully as yet, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is centrifugalized, centrifugal rotational speed and time are respectively 6000rpm and 3min; At last the deposition after centrifugal is carried out after with distilled water diluting more centrifugally, centrifugal rotational speed is 3000rpm, and the time is 3min.The deposition of centrifugal treating gained is disperseed with distilled water once more, and being configured to concentration is the Graphene mixed liquor of 0.5mg/mL.
Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on the quartz substrate, spin speed is 5000rpm, time 5min, and 70 ℃ of oven dry 2h are subsequent use in baking oven.The film that makes is the uniform light grey film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 72%, and conductance is 615S/cm.
Claims (10)
1. Graphene transparent conductive film, it is characterized in that: said Graphene transparent conductive film is the graphene film of 1 ~ 50nm, conductivity is 300 ~ 800S/cm, is 70 ~ 85% to wavelength at the light transmittance of the light of 200 ~ 1100nm.
2. the preparation method of a Graphene transparent conductive film may further comprise the steps: one, graphite oxide, press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer; Graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, and the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml, after stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, adds strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension; Add deionized water; Temperature of charge is brought up to 96 ± 1 ℃, react 1h, add 30% H again
2O
2, filtering precipitate does not have acid group with deionized water wash in filtrating, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake; Said strong oxidizer is potassium hyperchlorate and/or potassium permanganate; Two, preparation graphene oxide water mixed liquid adds graphite oxide filter cake, frequency 1-20KHz in pure water; Power 400-3000w, sonic oscillation 10-30min under the room temperature, centrifugal treating; Rotating speed is 500-6000rpm, and the time is 1-30min, removes the graphene oxide lamella more than 5 layers; Obtain the graphene oxide water mixed liquid, content is 0.01 ~ 1mg/mL; Three, the preparation graphene oxide film adopts spraying with graphene oxide liquid mixture, spin coating, and dip-coating is dripped coating method and on substrate, is obtained the graphene oxide film that thickness is 1-50nm; Four, adopt the method for high temperature reduction or electronation to obtain the Graphene transparent conductive film that thickness is 1 ~ 50nm.
3. the preparation method of Graphene transparent conductive film according to claim 2 is characterized in that: said obtaining is warming up to stirring reaction 3h between 30-40 ℃ behind the suspension, adds deionized water then.
4. the preparation method of Graphene transparent conductive film according to claim 2 is characterized in that: said graphite powder is a natural flake graphite, natural modified graphite; Delanium; In the expanded graphite more than one, its phosphorus content are>=90%, particle diameter D50<10 μ m.
5. the preparation method of Graphene transparent conductive film according to claim 2; It is characterized in that: said strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid; Concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.
6. the preparation method of Graphene transparent conductive film according to claim 2; It is characterized in that: said centrifugal treating is divided and is carried out for three times; Remove the graphite oxide filter cake of not peeling off fully as yet for the first time; For the second time supernatant liquor is centrifugalized, for the third time the sediment after centrifugal is centrifugalized after with distilled water diluting again.
7. the preparation method of Graphene transparent conductive film according to claim 2; It is characterized in that: said spraying is that substrate is preheating to 50 ~ 80 ℃; With spray gun graphene oxide liquid mixture is sprayed on the substrate, moisture content obtains graphene oxide film after volatilizing naturally; Said spin coating is to let substrate rotate with the 2000-5000rpm rotating speed; Time 5min; Graphene oxide liquid mixture is dripped on the substrate, graphene oxide liquid mixture is is evenly spread out and put at substrate surface, directly at 50 ~ 80 ℃ of dry 10min-2h; Naturally cool to room temperature then, obtain graphene oxide film after the drying; Said dip-coating is that substrate is immersed 5 ~ 60min in the graphene oxide liquid mixture, directly at 50 ~ 80 ℃ of drying 5 ~ 60min, naturally cools to room temperature then; Said is coated with is that the graphene oxide liquid mixture drop is directly dropped on the substrate, treat that graphene oxide liquid mixture is spread out and put on out fully after, directly, naturally cool to room temperature then at 50-80 ℃ of dry 5-60min.
8. the preparation method of Graphene transparent conductive film according to claim 2 is characterized in that: said high temperature reduction, vacuum environment; Or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen and acetylene gas, be in the reacting furnace of 5 ~ 10L at capacity, flow is 50 ~ 200sccm; Programming rate with 1-30 ℃/min; Be warming up to 200 ~ 1100 ℃, 0＜time≤7h, naturally cool to room temperature in the stove then; Electronation; Temperature is 70 ~ 90 ℃; Graphene oxide film is placed reducing agent steam, and in volume was the reaction vessel of 10 ~ 30L, steam flow was 20 ~ 200sccm; Time is no less than 1h, and reducing agent is more than one in hydrazine hydrate, hydrogen iodide, concentrated ammonia liquor, Dimethylhydrazine, sodium dithionite, sodium borohydride and the potassium borohydride.
9. the preparation method of Graphene transparent conductive film according to claim 8 is characterized in that: said nitrogen, argon gas, helium, temperature rise to 700 ~ 1100 ℃; Said hydrogen, acetylene, temperature rise to 200 ~ 700 ℃.
10. the preparation method of a Graphene transparent conductive film may further comprise the steps: one, graphite oxide, press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer; Graphite powder and anhydrous nitric acid sodium are joined the ice bath temperature in≤0 ℃ the strongly acidic solution, and the amount of strongly acidic solution is pressed the 1g graphite powder and is added 20 ~ 50ml, after stirring 30 ~ 60 minutes under the mixing speed of 30 ~ 600rpm, adds strong oxidizer; Continue to stir 2h, control reaction temperature is no more than 10 ℃, obtains suspension; Be warming up to stirring reaction 3h between 30-40 ℃, add deionized water, temperature of charge is brought up to 96 ± 1 ℃; React 1h, add 30% H again
2O
2, filtering precipitate, with deionized water fully wash until filtrating in do not have acid group, obtain water content by prior art vacuum dehydration then and be lower than 30% graphite oxide filter cake; Said graphite powder is a natural flake graphite, natural modified graphite, and Delanium, more than one in the expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m; Said strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%; Said strong oxidizer is potassium hyperchlorate and/or potassium permanganate; Two, graphite oxide reduces, and takes the method for high temperature solid-state reduction or liquid phase chemical reduction, obtains Graphene; Said high temperature reduction with the graphite oxide filter cake, directly toasts 2 ~ 10h down at 50 ~ 80 ℃, is crushed to D
50Be 1 ~ 20um; In vacuum environment, or in more than one atmosphere in the nitrogen, argon gas, helium, hydrogen, acetylene gas, be in 5 ~ 10L reacting furnace at volume; Gas flow is 20 ~ 200sccm; Directly high temperature reduction 10s ~ 10min in 900 ~ 1100 ℃ naturally cools to room temperature in the stove then, obtains Graphene; Said liquid-phase reduction is pressed graphite oxide filter cake, 80% concentration hydrazine hydrate mass ratio 0.7:1, and graphite oxide filter cake and hydrazine hydrate are mixed directly at 70 ~ 90 ℃; Rotating speed 30 ~ 100rpm, reaction reductase 12 ~ 10h obtains Graphene solution; Filter then and obtain Graphene; With pure water washing and filtering thing 3 ~ 6 times, obtain the Graphene slurries at last, obtain Graphene by the prior art drying; Three, the preparation of graphene film is mixed with the Graphene mixed liquor of 0.05 ~ 1mg/ml by Graphene, organic solvent, and the Graphene mixed liquor is adopted spraying, spin coating, and dip-coating is dripped a coating method and is obtained the Graphene transparent conductive film that thickness is 1 ~ 50nm; Said organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, butanone.
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